Triazine derivatives



Patented Jan. 8,, 1946 STAT s PATENT FFICE TRIAZINE DERIVATIVES vGaetano F. D'Alello and James W. Underwood Pittsfleld, Mass, assignorsto General Electric Company, a corporation of New York No Drawing.Application July 30, 1942, Serial No. 452,891

Claims. (Cl. 260-249.5)

' cerned with the production of new and useful arylsulfonylhydrazinoandhaloarylsulfonylhydrazino-substituted triazines. I

The chemical compounds of this invention may be represented by thefollowing general formula:

gum N N g nnm -gg l --(Na-Nn--som').

L N .E where n represents an intege and is at least i and not more than3, R represents a member 01' the class consisting of hydrogen andmonovalent hydrocarbon and substituted hydrocarbon radicals, moreparticularly halo-hydrocarbon radicals, and R represents a member of theclass consisting of aryl radicals and substituted aryl radicals, moreparticularly halo-aryl radicals.

Illustrative examples of radicals that R in the above iormula mayrepresent are: aliphatic (e. g.,

methyl, ethyl, propyl, isopropyl, butyl, secondary,

butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, octyl, allyl, methallyl,ethallyl, crotyl, etc.), including cycloaliphatic (e. g., cyclopentyl,cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aryl (e. g.,phenyl, diphenyl or xenyl, naphthyl, etc); aliphatic-substituted aryl(e. g., tolyl, xylyl, ethylphenyl,propylphenyl, isopropylphenyl,allyiphenyl, 2 butenylphenyl, tertiary butyl- Preferably R in Formula Iis hydrogen and n represents 1. The general formula for such a compoundis:

Preferably R in Formulas I andH is either a of, e. 8., methylol,methylene, etc., derivatives of the individual compound embracedby'Foi-mula I.

phenyl, etc); aryl-substituted aliphatic (e. g.,

benzyl, phenylethyl, cinnamyl, phenylpropyl, etc.) and their homologues,as well as those groups with oneor more of their'hydrogen atomssubstituted by, for example, a halogen, more particularly chlorine,bromine, fluorine or iodine. Specific examples or halogeno-substitutedhydrocarbon radicals that R in the above formula may represent are:chloromethyl, chloroethyl, chlorophenyl, dichlorophenyl, ethylchlorophenyl, chlorccyclohexyl, phenyl chloroethyl, bromoethyl,bromopropyl, iodophenyl, fiuorophenyl, bromotolyl; etc.;

Illustrative examples. of aryl and substituted aifyl radicals that R. inFormula I may represent are: phenyl, diphenyl, naphthyl, anthracyl.tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, 2butenylphenyl, tertiary butylphenyl, methylnaphthyl, ethylnaphthyl,iodophenyl, chlorophenyl, bromophenyl, fiuorophenyi,

- chlorotolyl, 'bromotolyl chloroxylyl, dichlorophenyl, iodotolyl,propenylphenyl, etc.

These new compounds are especially valuable in the preparation orsynthetic resinous compositions. Thus, they may be condensed with, forinstance, aldehydes, including polymeric aldehydes, hydroxyaldehydes andaldehyde-addition products, to yield condensation products of particularutility in the plastics and coating arts. Such condensation products aremore fully described and are specifically claimed in our copendingapplication Serial No. 452,890, filed concurrently herewith aud assignedto the same assignee as the present invention.

Various methods may be employed to produce the chemical compounds ofthis invention. We prefer to prepare them by effecting reaction, in thepresence of a hydrohalide acceptor, between a hydrazino-substituteds-triazine and an aryl suliouyl chloride, bromide or iodide, preferablyan aryl sulfonyl chloride or bromide.

Illustrative examples of hydrazlno trlazines that may be employed,depending upon the particular end-product sought, are;

z-liydrazino 4-methylamino 6-ethylamino s-triazine Hydrazinodi-(pentylamino) s-triazine Hydrazino di-(isobutylamino) s-triazinevHbrdrazino di-(propenylamino) s-triazine Hydrazino di-(butenylamino)s-triazine 'Hydrazino dixylidino s-triazine.

Hydraz'ino dl-(naphthylamino) s-triazine di-(ethylanilino) s-triazine-Mono-(cyclohexenylamino) di-(hydrazino) s-triazlne Y I Hydrazinodi-(phenethylamlno) s-tria'zin Hydrazino di-(cinnamylamino) s-triaaineHydrazino di-(chloromethylamino) s-trl'azlne Hydr'azinodi-(bromoethylamino) s-trlazine Hydrazino' di-(chloroanilino) s-triazine-Hydrazino di-(bromotoluido) s-triazine Hydrazino di- (fluoroanilino)s-triazine Hydrazino di-(iodotoluido) s-triazine Mono-(octylamlno)di-hydrazino) -,s-triazine Mono-(benzylamino) di-(hydrazin'o) s-triazineIllustrative examples of monoand poly-aryl sulfonyl halides-that may beused, dependingupon the desired endproduct, are:

Benzene sulfonyl chloride Benzene sulfonyl bromide Benzene sulfonyliodide Toluene sulfonyl chloride Toluene suli'onyl bromide xylenesulfonyl chloride Ethylbenzene sulionyl chloride Propylbenzene sulfonylchloride Isobutylbenzene sulfonyl chloride Propenylbenzene sulfonylchloride Diethyl benzene sulionyl chloride Methyl ethyl benzenesulfonyl'chloride Naphthalene sulionyl chloride Anthra'cene sulfonylchloride phlorobenzene sulfonyl chloride Chlorobenzene sulfonyl bromideBromobenzene sulfonyl chloride Dichlorobenzene sulfonyl chlorideBromotoluene sulfonyl chloride. Chloroxylene sulfonyl chloride Variouslwdrohalide acceptors may be employed, the chosen acceptor dependinglargely upon the particular solvent used. We prefer to use as thehydrohalide acceptor a tertiary base, 9. g., trialkyl amines such astrimethyl amine, triethyl amine, tributyl amine, etc., triaryl aminessuch as triphenyl amine, tritolyl amine,

etc., dialkyl aryl amines, e. g., dimethyl aniline, etc., pyridine,quinoline, etc.

The reaction between the hydrazino-substi tuted s-triazine and the arylsulionyl halide may be carried out in any suitable manner but preferablyis effected in the presence of a suitable anhydrous solvent or mixtureoisolvents, e. g..

' ether, benzene, toluene, etc. The choice of the solvent dependslargely upon economic considerations and upon the solubility of thestarting reactants. The reaction may be carried out at "that. instead ofbenzene sulfonyl chloride, an

asoaeao normal, sub-normal or at elevated temperatures and atatmospheric, sub-atmospheric or superatmospheric pressures. We prefer tocarry out the reaction at normal temperatures and pressures.

The above reaction may be represented by the following general equation:

In the above equation X represents a halogen. selected fromthe classconsisting of chlorine, bromine and iodine, and n, R and B have the samemeanings as given above with-reference to Formula I. v

In order that those skilled in. the art better may understand how thepresent invention may be carried into efiect, the following examples aregiven by way of illustration and not by way of limitation. All parts areby weight.

exam le 1 I This example illustrates the preparation of (benzenesulfonyl hydrazino) diamino s-trlazine, the. formula for which is Thebenzene sulfonyl chloride was dissolved in the ether and the resultingsolution then was added slowly to the mixture. of the other componentswhile stirring vigorously and cooling. After standing for 1 hour at roomtemperature, the reaction mass was shaken for 4 hours at thattemperature. After standing for -65 hours at room temperature theprecipitate comprising (benzene sulfonyl hydrazino) diamino s-triazinewas filtered ofl, washed with ether and dried. A yield of 184 parts ofthe purified product was obtained.

Example 2 triazine, an equivalent amount of hydrazino di- (methylamino)s-triazine is employed.

' Example 3 (Toluene sulfonyl hydrazine) diaminos-tria zine is preparedin essentially the same manner as described, under Example l'with-theexception aaeaese I i 3 equivalent amount of toluene sulienyl chlorid(Toluene sulienyl hydrazine) -di-.'.(einn1 mla1lllis used. a 1 v no)s-triaziue As it will be readily understood by those skilled z benzenesuifonyl hydrazine) d-chleromethylin the art, when it is desired toproduce cem- I amine fi-methylao 3- aim pounds containingasingle amine(-NI-IR) group, 8 (Benzene 'sulfenyl hydrazine) di-(chleroethyling. andtwo arylsulfonylhydrazine'er halearylamino) s-trie l 'sullenylhydrazinegroupings attached to the tri- Di-(teluene sulfenyl hydrazine)fi-methylamine azine nucleus or a compound containing three s-triazinearylsulfenylhydrazine erhalearylsulfonylhydrafi-benrenesulrenylhydrazino 4 teluenesulienylzinegroupings attached to the triazine nucleus, 10 hyneo-ethylbenzenesulfonylhyo sthen the starting reactants and proportionsof trie reactants are chosen so as to yield the desired (Toluenesulfenyl hydrazine) di-(iedeaniline) products in accordance with methodssuch as s-triazinc above given by way of illustration. For example,(Chlerobenzene sulienyl hydrazine) diamine sin the preparation 01meneamine (ii-(benzene triazlne i v sulienyl hydrazine) s-triazine thereis used (Brometoluene sulienyl hydrazine) diamine smenoaminedi-(hydrazine) s-triazinein an equiv triazine valent amount to thatshown in Example 1 with (Iedebenzen'e sulfenyl hydrazine) di-(methyl-ireference to hydrazine diamino s-triazine, and amine) s-triazine benzenesulienyl chloride and pyridine in twice 2o (Fluorebenzene sulfenylhydrazine) di-(ethylthe amounts there mentioned. Similarly, in theamine) s-triazlne preparation 0! tri-(benzene sulienyl hydrazine)(Benzene sulfenyl hydrazine) di-(cyclohexyls-triazine there is usedtri-(hydrazino) s-triazine amine) s-triazine in an equivalent amount tothat shownin Ex- (Toluene sulienyl hydrazine) di-(cyclehexenvlample 1with reference to hydrazine diamine amino) s-triazine s-triazine, andbenzene sultonyl chloride and In a manner similar to that describedabove pyridine in three timeathe amounts there men with particularreference to the arylsulfenyltiened. hydrazineandhaloarylsulfonylhydrazine-sub- Other examples of chemical compoundsemstituted symmetrical triazines (s-triazihes), ceribraced by FormulaI'that may be p'reduced'in responding derivatives of the asymmetricaland accordance with the present invention are listed vicinal triazinesmay be prepared. below: What we claim as new and desire to secure by(Benzene suuonyl hydmmm) m (ethylam-mo) Letters- Patent of the UnitedStates is:

s-triazine 1 Z-(benzene sulfenyl. hydrazine) t inethylamine generalformula B-amino s-triazine 1 1 2-(benzene sulrenyl hydrazine) aminos-trlazlne 2-(benzene sulionyl hydrazin' methylamine s-triazine db 1 vfii g g gfix ig gfigg g ggfim where n represents an integer and is atleast 1 (Xylene sullenyl hydrazine) diamine s tri'azine and not morethan R represents a member Amino (ii-(Xylene sulienyl hydrazino) 841mm:of the class consisting of hydrogen and moneva- Tmmylene sulfonylhydrazmo) .s tflazme lent hydrocarbon and hale-hydrecarbon radicals.

N h h and R represents a member of the class consistap t alene sulienylhydrazine) diamine s mg of aryl and halmaryl radicals.

triazine Amine (ll-(naphthalene sulionyl hydrazine) s- Chemicalcompounds as in claim 1 wherein m m R represents hydrogen.

Tri-(naphthalene sultonyl hydrazine) s-triazine P chemical compounds-as9 1 wherein (Toluene sulfenyl hydrazine) di-(methylamino) presents anaryl radical ktriazine 4. Chemical compounds as in claim 1 wherein(Benzene suli'enyl hydrazine) dianiline s-triazine radical (Xylenesulfonyl hydrazine) dianilino strlazine (Propymenzene suuonyl hydrazine)dbmentyb 5 5. A mene- (aryl sulfonyl hydrazine) diamine amine)s-trlazine s-triazine. I (Pr penylbenzene sulienyl hydrazine) di-(ise-(Benzene m'l hydrazine) diamine s-trlbutylamine) s-triazine wine.

(Diethylbenzene sulfonyl hydrazine) diteluide s g g 1 sulfonylhydra-Z130) s-triazine (Benzene sulienyl hydrazine) di-(butenyl m A tri-(aryl sulfenyl hydrazine) s-triazine.

5411mm} 9. The method of preparing chemical c m- (Anthmmne. suuonylhydrazine) I dlxynmno 5? pounds corresponding to the general formulatriazine i (Toluene sulfenyl hydrazine) dl-(naphthyl- N/ \N amine)s-triazine R.

(Methyl ethyl benzene sulionyl hydrazine) di- EN it NHNH SOR')'(phenethylamine) s-triazine (Biriiiziegeinsilfenyl hydrazine)di-(chlereaniline) 233 2, reprezgnts gnnmteger and is at least 1 no morean re (Telireinzusulfenyl hydrazine) di-(brometeluide) the classconsisting f g i g'l g fz fiszf g sa e a hydrocarbon and hale-hdrecarben di (Toluene sulfenyl hydrazine) di-(ethylanilino) R,represents a, membe: of the 519;: 02:53:32 s-trlazine of aryl andhalo-aryl radicals, said method cem- 1. Chemical compounds correspondingto the R represents hydrogen and R. represents an arylprisingefleetingreactiemintheota hydrehaiide acceptor. between (1) acompound corresponding to the general formula v where n and B have themeanings above given,

and (2) a compound corresponding to the general formula n(R.'-SO:X) Iwhere X represents a halogen selected irom the class consisting ofchlorine, bromine and iodine, and n and R have the meanings above given.

10. A method as in claim 9 wherein the hydreeiiecting reaction, in thepresence of a hydroh'alide acceptor, between approximately equimolecularproportions of hydrazine diamino s-triazine and benzene sulfonylchloride.

13. A method as in claim 12 wherein the hydrohalide acceptor is pyridineand the reaction is carried out in the presence of an' anhydrous selventwhich is inert to the other ingredients present in the reaction mass.

14. The method of preparing (benzene sulionyl hydrazine) diaminos-triazine which comprises eiiecting reaction, in the absence of appliedheat, between hydrazine diamino s-triazine and benzene sulionyl chloridewhile admixed with pyridine, said hydrazine diamino s-trlazine, benzenesulfonyi chloride and pyridine being employed in approximatelyequimolecular proportions, and said benzene sulienyl chloride beingdissolved in ether before being brought into contact with the hydrazinediamino s-triazine and pyridine, and isolating and purifying the(benzene suli'onyl hydrazine) diamino s-triazine 'fonyl chloride andpyridine being employed in approximately equimeleoular proportions, and,after a reaction period of the order of 70 hours at. room temperature,filtering of! the resulting Y precipitate comprising (benzenesulfonylhydrazine) diamine s-triazine, washing the said precipitate withether, and drying the washed pre cipitate;

' GAETANO F. DALELIO. JAMES W. UNDERWOOD.

